DE703900C - Process for the production of capillary-active bindings of aminoarylsulfonic acids - Google Patents

Description

Process for the preparation of capillary-active derivatives of aminoarylsulfonic acids It has been found that valuable capillary-active substances are obtained when organic Hydroxyl compounds of the general formula R-Ar-OH, in which the radical R at least a radical containing at least three carbon atoms and the radical Ar is one aromatic radical means with functional derivatives of nitroary1sulfonic acids, in particular their halides, brings them to reaction, in the reaction products obtained the nitro group is reduced to the amino group and water-solubilizing at the amino group Introduces remnants. According to one embodiment, the method can also be carried out in the manner that one uses the organic hydroxyl compounds instead of the functional derivatives the nitroarylsulfonic acids and the subsequent reduction of the nitro group to Amino group directly with functional amino or acylaminoarylsulfonic acid derivatives converts and in the reaction products obtained on the amino group, if necessary after cleavage of the acyl radical, - introduces water-solubilizing radicals.

In the general formula R-Ar-OH, the radical R means one or several aliphatic, cycloaliphatic or fatty aromatic radicals .. As aliphatic Remnants come e.g. B. propyl, amyl, octyl, dodecyl, hexadecyl or branched Residues such as isopropyl, the various isohexyl, isodecyl, isotetradecyl, Isooctadecy 1- and the like radicals, or radicals with tertiary carbon atoms, such as Tertiary butyl, tertiaryamyl, diisobutyl, triisobutyl, tertiary ethylhexyl Test, into consideration. As cycloaliphatisclie, or fatty aromatic radicals are, for. B. Cycloliexyl or. -llkyicycloliexvlreste, the tetrahydro- and decahydronaplitylrest, the benzyl-, menaplitliyl- and Tetrahydroinetiaplitliylrest to be mentioned. Those represented by the radical R. Residues can optionally also contain other atoms or groups of atoms, such as halogen, Oxygen, sulfur or nitrogen or their known combinations.

The radical Ar is to be understood as an aromatic radical, like the rest of benzene, toluene, xylene, naphthalene, phenanthrene, antracene, diplienyls, Diplienyläthans, Diplienylmethans, PlienyInaphthvlmetlians and the like in turn by hydrocarbon residues of all kinds, such as. B. methyl or ethyl groups, be substituted directly or via an oxygen or a sulfur atom. You can also have substituents such as halogen, llydroiyl and nitrogen groups, contain.

The organic hydroxyl compounds of the general formula R - Ar - O H are obtained by condensation of primary, secondary or tertiary alcohols or their mixtures or the olefins corresponding to these alcohols with aromatic ones Components such as phenols, naphthols and the like. Obtained. The condensation takes place in a manner known per se, optionally using suitable catalysts, such as inorganic acids, metal halides, boron fluoride and its addition products, Surface catalysts.

Starting materials can be used in the preparation of these hydroxyl compounds use, which the technology makes available in part on a large scale, such as z. B. the reduction from vegetable, animal or mineral fats or waxes obtainable higher molecular weight aliphatic alcohols or the napthenic alcohols, the resin alcohols obtained by reduction from natural resins and resin acids, also Petitylmetlivlcarbinol, ij-Ätlivlbutylalkohol, p-Äthylhexy lalkoliol, ß-Butvloctvlalkohol, -% ethyl isobutyl carbinol, turpentine oil, pine oil, alcoholic and olefinic products charring, tailings from methanol synthesis, olefinic products from Lignite smoldering, the cracking of crude oil and paraffins as well as the synthesis of gasoline.

To kertialkylated aromatic hydroxyl compounds with unbranched The alkyl chain can be obtained by using carboxylic acids or their derivatives esterified with aromatic oxy compounds, the esters in a known manner to the corresponding oxyaryl ketones and optionally the ketone groups therein converted into a methylene group by reduction. According to the invention with these Functional derivatives brought to reaction with organic hydroxyl compounds of nitroary sulfonic acids are, for example, anhydrides, methyl or ethereal esters, Azides and especially halides of these sulfonic acids. The nitroarylsulfonic acid halides correspond to the general formula (, Hal - S 0,) n - Ar - (\ 0,) m. in the hal one Halogen atom and Ar an aromatic radical, such as the rest of benzene, naphthalene, Phenanthrene, Anthracene, Dipheily1s, Diphenylmethane and the like, means which also substituents, such as hydrocarbon radicals of all kinds, e.g. B. methyl, ethyl u. Like residues that can be bonded directly or via oxygen or sulfur, Halogen, hydroxyl groups, etc. may contain. n or in denotes the number i or a higher number.

These nitroarylsulfonic acid halides are obtained according to known methods Methods, e.g. B. by the action of chlorosulfonic acid on the nitroaryl compounds or by treating nitroarylsulfonic acid salts with phosphorus pentachloride or chlorosulfonic acid. According to the invention, for. B. the following N itroarvlsulfonsäurehalogenide the following are used: 3-nitrobenzene-i-sulfochloride, 5-nitro-2-chlorobenzene-i-sulfochloride, 3-Nitro-4-chlorobenzene-i-sulfocuran, 3, 5-dinitrobenzene-i-sulfoclilorid, 2-nitrotoluene-4-sulfochloride, 4-nitrotoluene-2-sulfochloride, 5-nitronaphthalene-i-sulfochloride, 4-nitronaphthalene-2, ö-disulfocliloritl, 4 '- \ titrodiphenyl-4-sulfochloride.

Instead of the functional derivatives of nitroarylsulfonic acids according to a special embodiment of the method usable functional Derivatives of aminoarylsulfonic acids, in particular anliiloarylsulfonic acid halides, obtained by known processes by the action of chlorosulfonic acid on amino sulfonic acids. The corresponding alkylaminoarylsulfonic acid halides are known in the art by treating aromatic acylamines with chlorosulfonic acid or with acylaminoarylsulfonic acids accessible with chlorosulfonic acid or phosphorus pentachloride.

The conversion between the functional derivatives of nitroarylsulfonic acids, in particular their halides, and the organic hydroxyl compounds of the formula R - Ar - O H takes place in a known manner. One leaves the metal compounds, in particular Alkali metal compounds, the organic hydroxyl compounds expediently in the presence suitable solvents or diluents, such as benzene, xylene, chlorinated hydrocarbons u. Like., act on the Nitro.arylsulfo.nsäurehalogenide, optionally with use suitable acid-binding agents, such as alkalis, calcium oxide, barium oxide, sodium acetate etc. You can also use pyridine as an acid-binding agent, with but not from the metal compounds of the organic hydroxyl compounds, but emanates from these compounds as such. The metal halides formed during the reaction are eliminated. After isolation of the reaction products containing nitro groups these are subjected to reduction on the nitro group, which is more common MethGden served, e.g. B. the reduction with alkali sulfides, using zinc or iron in the presence of _ hydrochloric acid, common salt, glacial acetic acid, etc., or catalytic hydrogenation, where appropriate solvents or diluents, such as. B. alcohol, Glacial acetic acid and the like, can also be used.

If one goes directly according to a special embodiment of the method from functional derivatives of amino- or acylinoarylsulfonic acids the implementation of these compounds, in particular the halides, according to the same known methods. The activation of a reduction stage is not necessary here, only the acyl group which may be present must be carried out before further treatment be split off at the amino group by saponification.

The amino compounds obtained, which correspond to the general formula (R-Ar-O-O, S) 1, -Ar- (NH2) Q (n or m = i or a higher number), are now on the amino group with such Treated agents that are able to make the entire molecule water-soluble. Methods known per se are used for the introduction of such residues. . You can, for example, by treatment with several moles of allylene oxides, such as. B. Ethylene oxide, glycide and the like., Polyether or polyoxy ether groups introduce. can Halogenallzy lsulfuric acid ester, haloalkyl: sulfonic acids or carboxylic acids and haloalkylaryls: sulfonic acids, such as 2-chloroethyl-sulfuric acid ester, i-Clilorhex3-1-6-sulfuric acid ester, mono- or disulphuric acid ester of chlorohydr ine polyhydric alcohols, z. B. of glycerine, zC.hlorätliansulfonsäure, benzylchloride-.l.-sulphonic acid and the like. Can also produce the corresponding acidyl derivatives with halocarboxylic acids or their functional derivatives with subsequent replacement of the halogen atom by water-solubilizing groups, such as - S 03 H , - S - S 03 H, quaternary ammonium or betaine groups, or can also allow betaines to act directly; Furthermore, the water solubility can also be achieved by partial acidylation with polybasic carboxylic acids or sulfocarboxylic acids, e.g. B. sulfoacetic acid, sulfophthalic acid and the like, and can finally convert the amino group into a water-soluble quaternary ammonium group by exhaustive alkylation.

The products obtained by the present process have pronounced surface active properties and are known in the art, e.g. B. in detergent, Textile, leather, tobacco products and paper industries, with advantage as netting, washing, R: cleaning, emulsifying and dispersing agents can be used.

One has already alkylated aromatic sulfonic acids from phenols u. Ä. Aromatic Oxyv compounds used as soap substitutes. These products but do not have any washing power, but only show a certain wetting effect. Furthermore, one already has aromatic oxy compounds containing higher molecular radicals, . that contain carboxyl groups have been proposed as capillary-active substances. Although these fabrics have washing properties, they are not lime-resistant. In contrast the condensation products of the present invention are characterized by high detergency as well as good lime resistance. They are also due to their special constitution as aryl sulfonic acid ester, particularly stable to alkaline agents with which they are can be used together. Example i 24 parts by weight of the sodium compound des selc.-octyl-o-cresol, which in a known manner by condensation of i,: 2-octene and o-cresol is obtained, and zao parts by weight of 3-nitrobenzene-i-sulfochloride are obtained in the presence of a diluent, such as xylene, for several hours with stirring treated in a water bath. The reaction product obtained is of the same time Freed \ atrium chloride formed and worked up in the usual way.

Zoo parts by weight of the reaction product are now converted into 1,000 parts by weight Glacial acetic acid subjected to reduction with zinc dust at room temperature, whereupon the formed Aminov connection of the formula sec. Cs H17 # C, H3 (C H3) # O # S O. # C, H., # N H. = is isolated in a known «\ # @ - iron.

187 parts by weight of the amino compound obtained are heated under pressure with i; io parts by weight of sodium f-bromoätlivlscliwefelsaurem in an alcoholic medium in the presence of sodium acetate. Entry of the ethylsulfuric acid ester salt residue takes place at the amino group with the formation of a is worked up in the usual way. The salt is water-soluble and has soap properties in an aqueous solution.

Example 2 250 parts by weight of the N atriuniverbverbindungen of a mixture of isoalkyl cresols, which by condensation of techn. Cresol and a synthetic hydrocarbon fraction obtained from carbon oxide and hydrogen (containing hydrocarbons with 6 to 14 carbon atoms, average mol. Wt. 107, JZ 8.1 ) was obtained, and 271 parts by weight of 5-nitroaphthalene-i-sulfochloride are condensed as in Example i. The reaction product obtained is subjected to reduction with zinc dust and glacial acetic acid, whereupon the amino compound formed is worked up in the usual way.

2i5 parts by weight of this amino compound are in the autoclave under Stirring in the presence of 100% caustic soda treated with 33o parts by weight of Ätlivlenoxvd. It is heated at 120 to 130 ° until there is no longer any significant pressure is. The condensation product obtained is worked up in Das; it is water soluble and shows soap properties in aqueous solution. speaking amount of alkali bromide. The sodium salt obtained by this reaction of the formula

Claims (2)

PATENT CLAIMS: i. Process for the production of capillary-active Derivatives of aminoarylsulfonic acids, characterized in that organic Hydroxyl compounds of the general formula R-Ar-OH, in which R at least one radical containing at least three carbon atoms and Ar an aromatic radical means with functional derivatives of Nitroary1sulfonsäuren, especially their Halogenides, brings to implementation, the nitro group in the reaction products obtained reduced to the amino group and water-solubilizing residues introduced on the amino group. 2. The method according to claim i, characterized in that one for the reaction with the organic hydroxyl compounds of the formula R-Ar-O H instead of the functional ones Nitroarylsulfonic acid derivatives directly functional amino or acylaminosulfonic acid derivatives used and optionally in the reaction products obtained on the amino group after cleavage of the acyl radical introduces water-solubilizing radicals.